Acrylic acid esters

ABSTRACT

Monomeric compositions which are the reaction product of a monoamine or a polyamine having from two to four amino nitrogen atoms. Such reaction products may be characterized by the following general formula:   WHEREIN X IS AN INTEGER FROM 0 TO 3; Y IS AN INTEGER FROM 0 TO X; R1 and R2 are selected from the group consisting of acryloyloxy and methacryloyloxy; R3, R4, R5, R6, R7, and R8 are selected from the group consisting of hydrogen and lower alkyl; R9 and R10 are selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, lower hydroxyalkyl acryloyloxy, and lower hydroxyalkyl methacryloyloxy; and R11 is a lower alkylene group linking two nitrogen atoms.

United States Patent 11 1 Manaka 1 ACRYLIC ACID ESTERS [75] Inventor:

[73] Assignee: Broadview Chemical Corporation,

Broadview, Ill.

Sept. 24, 1969 Kazuo Manaka, Broadview, Ill.

[22] Filed:

21 Appl. No.2 860,786

52 US. c1.... 260/486 R, 117/124 E, 117/161 02,

[51] Int. Cl. C07c 69/54 [58] Field of Search 260/486 R [56] References Cited UNITED STATES PATENTS 2,458,422 1/1949 Reynolds et al. 260/486 R 3 4l7,567 12/1968 Higashimura 260/41 A Primary Examiner-L0rraine A. Weinberger Assistant Examiner-Paul J. Killos 1 Feb. 25, 1975 [57] ABSTRACT Monomeric compositions which are the reaction product of a monoamine or a polyamine having from two to four amino nitrogen atoms. Such reaction products may be characterized by the following general formula:

R R R R 7 R R R 011 3 Claims, N0 Drawings ACRYLIC ACID ESTERS The present invention relates to a novel composition of matter, and more specifically to a novel monomeric composition and to the polymers prepared therefrom.

Generally, the monomer of the present invention may be characterized as the reaction product of an unsaturated epoxy compound and a monoamine or a polyamine having from two to four amino nitrogen atoms. Such reaction products may be characterized by the follewirtg .se srstfermub;

wherein x is an integer from O to '3; y is an integer from to x; R, and R 'are selected from the group consisting of acryloyloxy and methacryloyloxy; R R R R R and R are selected from the group consisting of hydrogen and lower alkyl; R9 and R10 are Se ected from th v character, the compositions of the present invention group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, lower hydroxyalkyl acryloyloxy, and lower hydroxyalkyl methacryloyloxy; and R is a lower alkylene group linking two nitrogen atoms.

In the preferred embodiment, R and R will have terminal unsaturation, i.e., a double bond adjacent to the end carbon atoms on the molecule.

A particularly preferred composition in accordance with the present invention is the reaction product obtained by reacting glycidyl acrylate and/or lower alkyl acrylates with monoamines and polyamines. For example, when a lower alkyl or hydroxyalkyl monoamine is employed, a product of the following structure is ob- I OH R OH wherein R and R are selected from the group consisting of hydrogen and lower alkyl, and R is selected from the group consisting oflower alkyl, lower hydroxyalkyl, cyano, and lower cyanoalkyl.

In a particularly preferred embodiment, glycidyl methacrylate is reacted with isopropyl amine, so that R, and R are methyl, and R is isopropyl. If it is desired to enhance the water solubility of the product, an alkanolamine may be employed, so that R is a hydroxyalkyl group.

Particularly preferred diamine and polyamine derivatives are prepared in accordance with the present invention by reacting glycidyl acrylate and/or lower alkyl acrylate with a suitable diamine or polyamine, to obtain a product having the following general formula:

R OH

10 that may be prepared by reacting the monomers of the present invention with an acid.

As a result of the u nsaturation that is present, the

compositions of matter in accordance with the present invention have great utility as monomers. The functionality of the monomers is enhanced by employing a polyamine (i.e., where x is l or more). Because of its polar are also useful as surface active agents and as antistatic agents.

The present invention also relates to polymers prepared by reacting the foregoing monomers with suitable curing agents such as hydrogen peroxide or an ortion is the presence of hydroxyl groups along the monomer molecule. These hydroxyl groups contribute a polar character to the monomer, producing a high bond strength when polymers made therefrom are used irrthebonding of metals. This bond strength is still further increased when the nitrogen atom has a hydroxyal kyl, cyano, or cyanoalkyl group bonded thereto.

Polymerization of the monomers of the presentinvention may be inhibited with conventional polymerization inhibitors, such as hydroquinone, substituted conditions in the presence of an organic peroxide or hydroperoxide.

Particularly stable compositions may be prepared in accordance with the present invention by combining the monomers with other monomers and polymers,

such as a novolak (phenolformaldehyde) resin. Such em -time thong-R14 R5 )ytti fgCH -CI-P-Ct-lrO-fl-1=CH l H 3 14 H wherein R and R are hydrogen or lower alkyl, R, and R are selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, cyano, lower cyanoalkyl, and radicals of the formula monomers not only have great shelf stability, but also may be set up to form polymers of exceptionally high strength.

Examples of suitable unsaturated epoxy compounds 3 8 6 8 ,409 3 4 that may be reacted with amines to prepare the monomers of h P im!!! nvsqtismarqa i law;

. o glycidyl acrylate CH CH A O" CHTW -JCHQ glycidyl me thacrylabe CH -'O-CH -CH-CH allyl glycidyl maleate l 5 CH OH CHQ-O-C CH=CHJOH WH allyl glycidyl phthalate I CH2 *CHPWHQ allyl-2,3-epox rbutyrate butadiene monoxide CH a CHr-CI-FZjI-I Suitable monoamines and polyamines for use in accordance with the present invention areas follows: 40

meth lamine OH NH y 3 2 ethylamine I C H NH iso r0 lamine CH CHNH Q-aminoethanol KOCH CH NH aniline v d a H hy zlne 2 NR phenylhydrazine N'HNH b isphenylhydrazine ethylene diamine diethylene t riamine menthane diamine m-phenylene diamine triethylene tet ramine t -diaminodipheny1methane 4, l -diaminodiphenylsu3fone cyanamide dicyandiamide aminomethyl cyanide aminoebhyl cyanide N-aminoethylpipe raz ine As those skilled in the art will realize, the number of unsaturated epoxy compounds and amines that may be used in accordance with the present invention is virtually unlimited.

7. wh anam ns is e sted t B.. FFl. PQ?FY CH I 3 m NH -c- N-CH -CH HNLJ 2 2 2 compound in accordance with the present invention. the epoxy ring is broken, producing a di-unsaturated or poly-unsaturated amine monomer. The reaction may be illustrated as follows, between glycidyl methacrylate and isopropyl amine:

III

It can be seen that this monomer has four carboncarbon double bonds, and thus is capable of a high de gree of cross-linking when polymerized.

As the reaction is exothermic, the monomers of the present invention are produced by simply mixing the appropriate amine and unsaturated epoxy compound. The amine salts are similarly prepared by an exothermic reaction.

As previously mentioned, when the amine salt derivalO tives of the present invention are combined with hydroperoxide or peroxide curing agents under acidic conditions, it has been found that hydroquinone and its derivatives actually act as curing accelerators, rather than an inhibitor, as would normally be expected. Alkyl hy- OH CH OH In the most preferred embodiment of the present invention, the amino monomers are further reacted with an acid, preferably an unsaturated organic acid, in order to produce the amine salt. It has been found that the monomers of the present invention have particu- I l ll y H OH larly advantageous properties under acid conditions.

The use of an unsaturated acid also has the advantage of introducing further unsaturation into the monomer.

CAI-l9 y droquinones are more active in this respect than unsubstituted hydroquinones, the amount of acceleration being proportional to the size and number of substituent vgroups. For example, the following hydroquinones have been arranged in increasing order of curing speed.

Thus, hydroquinones may be employed as a component of the monomer to extend shelf life, while at the same time serving as a polymerization promoter when A particularly suitable acid for preparing amine salts of 40 the monomer is mixed with a curing agent.

the monomers in accordance with the present invention are acrylic and methacrylic acids.

When polyamines are substituted for monoamines in accordance with the present invention, compounds having a high degree of functionality are produced,

since each nitrogen atom may react with up to two unsaturated epoxy compounds. For example, if glycidyl methacrylate is reacted with ethylene diamine, the fol- Conventional amine promoters may also be used in conjunction with the present invention. These are especially useful under basic conditions, e.g., when the amine salt of the monomer is not being used, since hydroquinone and its derivates do not function as accelerators under basic conditions. Exemplary amine accelerators include N,N-dimethylaniline, phenylhydrazine, N-aminorhodanine, t-butyl carbazate, cyanoguanidine,

lowing compound is producedz v v 7 MM oxalyhydrazide, carbohydrazide, 1-

CH O W I 3 u H CH C --C O CH Us NOH CH NH CH O O CH 3 I! n l 3 GH -C-COOH -?H'-CH 1;l-CH -CH -I;FCH -?H-CH -O-C-CCH OH CIR (3H OH cnon c moa' I 5" O O l l C=O (i=0 l l C-CH C-CH n 3 n 3 CH2 CH CH O tative, the scope of the invention being determined by the appended claims.

EXAMPLE 1 moles of glycidyl methacrylate were placed into a 3-necked flask equipped with a thermometer, stirrer, and separatory funnel. 10 moles of isopropyl amine were placed in the separatory funnel. isopropyl amine.

was fed into the flask over a period of l hour, whil e t he contents of the flask were maintained below C. by

constant stirring and by dipping the flask into cold wa-' ter. After all of the isopropyl amine was added, stirring was continued for 7 hours while the temperature was maintained below 30C. At the end of this interval, the contents of the flask were transferred to a second flask, where they were maintained for nine days at room temperature, in order to complete the reaction.

EXAMPLE 2 The procedure of Example 1 was repeated, except that glycidyl acrylate is substituted for the glycidyl methacrylate. The reaction conditions and appearance of the product were also the same as in Example 1.

u. EXAMPLE? Example 1 was repeated, except that ethanolamine was substituted for isopropyl amine. The reaction in this instance was somewhat faster, and heat was evolved much more rapidly. The product was also more Soluble n w terthaetbea 9 th PIQXiQHiEXEEBPEE.

probably as a result of the presence of three hydroxyl groups along the molecule.

EXAMPLE 4 Example 1 was repeated, except that 30 moles of glycidyl methacrylate were used, and ethylene diamine was substituted for the isopropyl amine. in this instance, a tri-functional monomer, having the following structure, is produced.

Example 1 was repeated, except that cyanamide was substituted for the isopropyl amine. Because of the cyanide group, the monomer product has a high degree of' polarity.

EXAMPLE 6 Forty moles of glycidyl methacrylate were reacted with ten moles of triethylene tet'ramine in the same manner as described in Example 1. A tetrafunctional monomer was produced, wherein eachof the amino nitrogen atoms reacted with a glycidyl methacrylate molecule.

EXAMPLE 7 A novolak resin was prepared by reacting phenol with formaldehyde in the presence of a small amount of hydrochloric acid catalyst. 143 grams of this resin were dissolved in 20 moles of glycidyl methacrylate. Ten moles of isopropyl amine were added to this solution as in Example I. The compound obtained-was extremely stable because of the presence of thenovolak resin, and could be kept for a long period oftime without polymerization.

EXAMPLE 8 The monomer made ingccordance with Example I was found to have a viscosity of about 650 centipoises. One mole of this monomer was reacted with one mole o f rne thacrylic acid, and agitated, producing the amine 'achieved when equimolar amounts of amine and acid are employed.

EXAMPLE 9 49.5 grams of the monomer prepared in Example 1 were mixed with 49.5 grams of methacrylic acid, to form the amine salt. After the salt had cooled, one gram of di-tert-amylhydroquinone was added and dissolved. The hydroquinone derivative acts as an inhibitor to polymerization in this system, as shown by its stability during heating at 120F. for days.

In a second container, 4 grams of t-butyl peroxymaleic acid were dissolved in a solvent'consisting of 88 grams of methylene chloride and 8 grams of acetone.

A steel bolt was coated with this second solution, and the solvent were allowed to evaporate, leaving the .tbutyl peroxymaleic acid behind. Then, the first component, containing the monomer, was coated onto the threads, and a bolt was screwed into position. The nut and bolt were finger tight," meaning that they could not be unscrewed with the fingers, after about 3 minutes. After 24 hours, the torque of the bonded nut and bolt was tested according to specification Mil S-22473C, and found to be 35 foot-pounds. In additional tests, it was found that the torque was so great that the bolt was broken before the nut could be unscrewed.

The polymer was further tested according to the pinand-collar test as set forth in specifications Mil-- R-46082 (MR). The results showed that curing was complete after three hours, and that a static shear strength of about 5,500 psi was produced.

EXAMPLE 10 Example 9 was repeated, except that one gram of di-tcrt-butylhydroquinone was substituted for the di-tert-amylhydroquinone. The results were almost identical, except that the curing speed of the polymer was slightly slower.

12 EXAMPLE '1 1 Example 9 was repeated, except that the monomer prepared in Example 3 was substituted for the monomer prepared in Example I. The results were similar to those obtained in Example 1.

EXAMPLE 12 Example 9 was repeated, except that t-butylhydroperoxide was substituted for the t-butyl peroxymaleic acid. Comparable results were obtained, except that the curing speed was somewhat slower.

EXAMPLE 13 99.5 grams of the monomer prepared in Example 1 were combined with 0.5 gram ofa phenylhydrazine accelerator. In this instance, the monomer was not converted to the amine salt. This solution was found to be stable to heating at 82C. for 2 hours or at l20F. for 10 days. The second component was the same as in Example 9. A sheet of glass was coated with the second component by spraying from an aerosol can. After the solvent had evaporated, each sheet was coated with the monomer component, and the two sheets were then pressed together. The polymer set up within 15 minutes. After 24 hours, the sheets of glass could not be separated.

EXAMPLE I4 Example 13 was repeated, except that benzhydrazide was substituted for the phenylhydrazine. The results obtained were virtually identical.

Obviously, many modifications and variations of the present invention will occur to those skilled in the art, and it is intended to cover in the appended claims all such modifications and variations as fall within the true spirit and scope thereof.

I claim:

1. A monomer characterized by the formula:

ii; MH -O- H 2 wherein R and R are selected from the group-consisting of hydrogen and lower alkyl.

2. Monomers characterized by theformula:

.tii...

on on wherein R, and R are selected from the group consisting of hydrogen and lower alkyl and R is selected from the group consisting of lower alkyl and lower hydroxy alkyl.

3. A monomer characterized by the formula: 

1. A MONOMER CHARACTERIZED BY THE FORMULA:
 2. Monomers characterized by the formula:
 3. A monomer characterized by the formula: 